EP3119377B1 - Matériaux dentaires photopolymérisables à double polymérisation à base de dérivés de thio-urée et de bisacyldialkylgermanium - Google Patents

Matériaux dentaires photopolymérisables à double polymérisation à base de dérivés de thio-urée et de bisacyldialkylgermanium Download PDF

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EP3119377B1
EP3119377B1 EP15710542.0A EP15710542A EP3119377B1 EP 3119377 B1 EP3119377 B1 EP 3119377B1 EP 15710542 A EP15710542 A EP 15710542A EP 3119377 B1 EP3119377 B1 EP 3119377B1
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Prior art keywords
dental material
hydroperoxide
material according
bis
dental
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EP3119377A1 (fr
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Norbert Moszner
Peter Burtscher
Alexandros Gianasmidis
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Ivoclar Vivadent AG
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Ivoclar Vivadent AG
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
    • A61K6/62—Photochemical radical initiators
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
    • A61K6/61—Cationic, anionic or redox initiators
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/15—Compositions characterised by their physical properties
    • A61K6/17—Particle size
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
    • A61K6/64—Thermal radical initiators
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A61K6/889—Polycarboxylate cements; Glass ionomer cements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical

Definitions

  • the present invention relates to photopolymerizable and dual-curing dental materials which are particularly suitable for use as dental filling material or fastening cement.
  • Dental composites usually contain a polymerizable organic matrix and one or more fillers. In most cases, a mixture of monomers, initiator components, stabilizers and pigments is used as the polymerizable organic matrix, mixtures of dimethacrylates often being used as monomers. Such materials can be cured by thermal, redox-initiated or light-induced radical polymerization. Acid monomers are also increasingly being used for the production of dental materials. These give the materials self-etching properties and improve their adhesion to the natural tooth substance.
  • thermal initiators such as dibenzoyl peroxide (DBPO), or derivatives of barbituric acid, such as trimethylbarbituric acid
  • DBPO dibenzoyl peroxide
  • barbituric acid such as trimethylbarbituric acid
  • the peroxides are combined with amines such as N, N-dimethyl-sym.-xylidine or N, N-dimethyl-p-toluidine and the barbituric acid derivatives with per compounds such as potassium peroxosulphate or peresters. Both peroxides and barbituric acid derivatives have to be stored in the refrigerator due to their limited thermal stability.
  • ⁇ -diketones As photoinitiators for light-curing materials, ⁇ -diketones have proven themselves, such as camphorquinone (1,7,7-trimethylbicyclo [2.2.1] heptane-2,3-dione) (CQ) and 9,10-phenanthrenequinone.
  • Photoinitiators are usually used together with amines such as ethyl 4- (N, N-dimethylamino) benzoate as reducing agents used.
  • Dual-curing dental materials contain a mixture of a photoinitiator and a redox initiator system.
  • amines as an initiator component has a number of disadvantages.
  • the oxidation of the amine accelerators can lead to discoloration of the materials.
  • amines react easily with acidic substances and are therefore not stable in the presence of acidic monomers.
  • Redox initiator systems based on thiourea derivatives show very good acid stability.
  • the U.S. 3,991,008 and the DE 26 35 595 Al disclose polymerizable dental filling compounds based on methacrylate monomers which contain a hydroperoxide oxidizing agent as an initiator in combination with a substituted thiourea as a reducing agent.
  • a preferred oxidizing agent is cumene hydroperoxide
  • a preferred thiourea derivative is acetylthiourea.
  • the compositions should be distinguished by improved color stability and storability and should not require storage in the refrigerator. In addition, they should have an excellent hardening speed.
  • the US 2003/0134933 discloses two-component, self-curing root canal filling materials which are said to be characterized by high stability at temperatures of up to 60 ° C.
  • the materials contain a hydroperoxide in combination as an initiator with a thiourea derivative.
  • the thiourea-containing component can additionally contain an acidic compound.
  • Photoinitiators can be used to enable the materials in the upper part of the root canal to harden quickly.
  • the WO 03/057792 A2 describes the use of polymerizable urea and thiourea derivatives as reducing agents in redox initiator systems.
  • the urea or thiourea compounds in combination with a second reducing agent such as ascorbic acid or a non-polymerizable thiourea derivative, should provide high color stability and good storage stability and hardening properties.
  • the reducing agent is combined with an oxidizing agent and optionally a photoinitiator.
  • Copper salts and complexes are mentioned as suitable copper compounds, such as, for example, copper benzoate, copper di (methacrylate), copper acetylacetonate and copper naphthenate.
  • the EP 1 693 046 Al discloses dental compositions which contain a 2-pyridylthiourea derivative and a hydroperoxide as initiator system.
  • the compositions should be distinguished by a high acid tolerance and should be suitable for the production of acidic dental primers and adhesives. They can also contain customary photoinitiator systems.
  • the WO 2008/134024 A2 suggests the use of cumene hydroperoxide in combination with benzoylthiourea as an initiator system for acidic self-etching dental cements.
  • the effectiveness of this initiator system is not intended to be impaired by acidic monomers, but rather to be increased.
  • the compositions can additionally contain a photoinitiator.
  • the EP 2 233 544 A1 discloses two-component, polymerizable dental materials which contain a hydroperoxide, a thiourea derivative as a reducing agent and a vanadium compound as an accelerator.
  • the materials also contain a polymer of an ⁇ , ⁇ -unsaturated mono- or dicarboxylic acid. They should have good hardenability and stability.
  • monomolecular photoinitiators are used, such as, for example, the commercially available compounds 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide. These photoinitiators form radicals in a monomolecular elementary reaction, i.e. by breaking the bonds of the photoinitiator.
  • acylgermans have also been used as photoinitiators for dental materials.
  • the EP 1 905 413 Al discloses acylgermane, which can be activated with visible light in the wavelength range from 200 to 750 nm. These are characterized by a high reactivity and are therefore already active in low concentrations. They are stable in the presence of acidic monomers and do not lead to discoloration of the materials like conventional photoinitiators for the visible wavelength range. Acylgermane can be combined with conventional redox systems to produce dual-curing materials.
  • Cyclic acylgermanium compounds that are suitable as photoinitiators are off EP 1 905 415 Al known.
  • the invention is based on the object of providing dental materials which do not show any discoloration, which have a high storage stability at room temperature and are acid-stable and which, after curing, have improved mechanical properties, i.e. in particular improved oral and abrasion stability and durability.
  • materials are to be made available which harden well and allow easy removal of excess material and which have a low cytotoxicity.
  • dental materials which contain a combination of at least one thiourea derivative and at least one bisacyldialkylgermanium compound as an initiator for the radical polymerization.
  • Dual curing dental materials also contain a peroxide and preferably a hydroperoxide as an additional initiator component.
  • Thiourea derivatives preferred according to the invention are described in U.S. 3,991,008 (Column 2, line 35 to column 3, line 14) and in EP 1 754 465 A1 (Paragraph [0009]).
  • Particularly preferred thiourea derivatives are methyl, ethyl, allyl, butyl, hexyl, octyl, benzyl, 1,1,3-trimethyl, 1,1-diallyl, 1,3-diallyl, 1- ( 2-pyridyl) -2-thiourea, acetyl, propanoyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl and benzoyl thiourea, acetyl and hexanoyl thiourea being very particularly preferred.
  • Preferred bisacyldialkylgermanium compounds are in EP 1 905 413 A1 , EP 1 905 415 A1 and EP 2 103 297 A1 described, wherein Bisacylgermane according to the formula (II) of EP 1 905 413 A1 are particularly preferred.
  • Very particularly preferred bisacyldialkygermanium compounds are bisbenzoyldiethylgermanium, Bisbenzoyldimethylgermanium, bisbenzoyldibutylgermanium, bis (4-methoxybenzoyl) dimethylgermanium, and bis (4-methoxybenzoyl) diethylgermanium, with bis (4-methoxybenzoyl) diethylgermanium being most preferred.
  • Preferred hydroperoxides are 1,1,3,3-tetramethylbutyl hydroperoxide, t-butyl hydroperoxide, cumene hydroperoxide, pinane hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide and t-amyl hydroperoxide, cumene hydroperoxide being particularly preferred.
  • a mixture of a bisacyldialkylgermanium compound as a photoinitiator with a thiourea derivative enables improved curing of dental materials.
  • the materials according to the invention are characterized in particular by a high degree of hardening, high surface hardness and abrasion stability, good material stability in the presence of saliva and longevity.
  • Photopolymerizable dental materials are preferably in the form of one-component systems, i.e. in the form of a mixture that contains all of the components of the dental material. They only contain a photoinitiator as initiator and can be cured by exposure to light.
  • dual-curing dental materials also contain a peroxide, preferably a hydroperoxide, as the oxidizing agent.
  • Dual-curing materials are preferably in the form of two separate components, since otherwise premature curing would take place, the first component containing the (hydro) peroxide and the second component containing the thiourea derivative.
  • the thiourea derivative serves as a reducing agent (accelerator).
  • the components are accordingly also referred to as catalyst paste and accelerator paste.
  • the hardening of the dual hardening materials can be triggered by mixing catalyst and accelerator paste.
  • the composition is adjusted so that it remains workable for a few minutes (so-called processing time) after the pastes have been mixed, but hardens quickly after processing.
  • the processing and hardening times can be set primarily through the type and concentration of (hydro) peroxide, thiourea derivative and, if necessary, through the addition of other components such as transition metal redox catalyst and inhibitor.
  • the dental materials according to the invention contain a free-radically polymerizable matrix.
  • Radically polymerizable monomers or mixtures of radically polymerizable monomers are preferred as the polymerizable matrix, in particular one or more (meth) acrylates, particularly preferably a mixture of monofunctional and polyfunctional methacrylates, very particularly preferably of monofunctional and difunctional methacrylates.
  • Monofunctional (meth) acrylates are understood to mean compounds with one, and polyfunctional (meth) acrylates compounds with two or more, preferably 2 to 4, free-radically polymerizable groups.
  • Preferred mono- or polyfunctional methacrylates are methyl, ethyl, 2-hydroxyethyl, butyl, benzyl, tetrahydrofurfuryl or isobornyl (meth) acrylate, p-cumyl-phenoxyethylene glycol methacrylate (CMP-1E), bisphenol-A-dimethacrylate, Bis-GMA (an addition product of methacrylic acid and bisphenol A diglycidyl ether), ethoxy or propoxylated bisphenol A dimethacrylate, such as bisphenol A dimethacrylate SR-348c with 3 ethoxy groups or 2,2-bis [4- ( 2-methacryloxypropoxy) phenyl] propane, UDMA (an addition product of 2-hydroxyethyl methacrylate (HEMA) and 2,2,4-trimethylhexamethylene diisocyanate), TMX-UDMA (an addition product of a mixture of HEMA and hydroxypropyl methacrylate (HPMA) with
  • a monomer mixture which contains at least one low-volatility monomethacrylate, at least one highly viscous poly-, preferably difunctional, methacrylate and at least one low-viscosity poly-, preferably difunctional methacrylate.
  • low-volatility monomers are understood to mean compounds with a boiling point> 150 ° C. at normal pressure.
  • the boiling point can be determined e.g. with a distillation apparatus.
  • Highly viscous monomers are substances with a viscosity of ⁇ 5 Pa ⁇ s, preferably 5 to 10,000 Pa ⁇ s and particularly preferably 5 to 2,000 Pa ⁇ s
  • low viscosity monomers are substances with a viscosity of ⁇ 300 mPas, preferably 1 to 300 mPas. s and particularly preferably 30 to 300 mPa ⁇ s, the viscosity being determined with a capillary (low viscosity) or rotary viscometer (high viscosity) at a temperature of 25 ° C.
  • TMX-UDMA an addition product of HEMA and hydroxypropyl methacrylate (HPMA) with ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-m-xylylene diisocyanate (TMXDI)) and 1,6-bis [2-methacryloyloxyethoxycarbonylamino] -2,4,4-trimethylhexane (UDMA).
  • Preferred low-viscosity dimethacrylates which are used as thinner monomers are bismethacryloyloxymethyltricyclo [5.2.1.] Decane (TCDMA), glycerol dimethacrylate (GDMA) and, in particular, decanediol-1,10-dimethacrylate (D 3 MA).
  • TCDMA bismethacryloyloxymethyltricyclo [5.2.1.] Decane
  • GDMA glycerol dimethacrylate
  • D 3 MA decanediol-1,10-dimethacrylate
  • a particularly preferred low-volatility monomethacrylate is p-cumyl-phenoxyethylene glycol methacrylate (CMP-1E).
  • the dental materials according to the invention contain, in addition to the abovementioned monomers, one or more acid group-containing radically polymerizable monomers (adhesive monomers). These give the materials self-adhesive and / or self-etching properties.
  • Preferred monomers containing acid groups are polymerizable carboxylic acids, phosphonic acids, phosphoric acid esters, and sulfonic acids.
  • Preferred carboxylic acids are maleic acid, acrylic acid, methacrylic acid, 2- (hydroxymethyl) acrylic acid, 4- (meth) acryloyloxyethyltrimellitic acid, 10-methacryloyloxydecylmalonic acid, N- (2-hydroxy-3-methacryloyloxypropyl) -N-phenylglycine and 4-vinylbenzoic acid.
  • Preferred phosphonic acid monomers are vinylphosphonic acid, 4-vinylphenylphosphonic acid, 4-vinylbenzylphosphonic acid, 2-methacryloyloxyethylphosphonic acid, 2-methacrylamidoethylphosphonic acid, 4-methacrylamido-4-methyl-pentylphosphonic acid, 2- [4- (dihydroxyphacrylic acid or 2 - [4- (Dihydroxyphosphoryl) -2-oxa-butyl] -acrylic acid ethyl- and -2,4,6-trimethylphenyl ester.
  • Preferred acidic polymerizable phosphoric acid esters are 2-methacryloyloxypropyl mono- or dihydrogen phosphate, 2-methacryloyloxyethyl mono- or dihydrogen phosphate, 2-methacryloyloxyethylphenyl hydrogen phosphate, dipentaerythritol pentamethacryloyloxypropyl-pentamethacryloyloxyphosphate , 6- (methacrylamido) hexyl dihydrogen phosphate and 1,3-bis (N-acryloyl-N-propyl-amino) propan-2-yl dihydrogen phosphate.
  • Preferred polymerizable sulfonic acids are vinyl sulfonic acid, 4-vinylphenyl sulfonic acid or 3- (methacrylamido) propyl sulfonic acid.
  • Particularly preferred adhesive monomers are 4- (meth) acryloyloxyethyl trimellitic acid, 2- [4- (dihydroxyphosphoryl) -2-oxa-butyl] -acrylic acid ethyl or -2,4,6-trimethylphenyl ester and 10-methacryloyloxydecyl dihydrogen phosphate.
  • the dental materials according to the invention preferably also contain organic or particularly preferably inorganic particulate fillers.
  • Fillers based on oxides, such as SiO 2 , ZrO 2 and TiO 2 or mixed oxides of SiO 2 , ZrO 2 , ZnO and / or TiO 2 nanoparticulate or microfine fillers, such as pyrogenic silica or precipitated silica (weight-average particle size of 10 -1,000 nm) as well as mini-fillers such as quartz, glass ceramic or X-ray opaque glass powder from, for example, barium or strontium aluminum silicate glasses (weight-average particle size of 0.2-10 ⁇ m).
  • fillers are X-ray opaque fillers such as ytterbium trifluoride or nanoparticulate tantalum (V) oxide or barium sulfate or mixed oxides of SiO 2 with ytterbium (III) oxide or tantalum (V) oxide (weight-average particle size of 10-1,000 nm).
  • SiO 2 -based fillers can be surface-modified with methacrylate-functionalized silanes, such as 3-methacryloyloxypropyltrimethoxysilane.
  • methacrylate-functionalized silanes such as 3-methacryloyloxypropyltrimethoxysilane.
  • Functionalized acidic phosphates such as 10-methacryloyloxydihydrogen phosphate, can also be used to modify the surface of non-silicate fillers, for example ZrO 2 or TiO 2.
  • Dental materials containing fillers are particularly suitable as dental filling composites and cements. Particularly preferred are materials that only contain fillers with a maximum particle size of less than 600 nm. These are particularly suitable as dental cements.
  • compositions used according to the invention can optionally contain further additives, especially stabilizers, such as, for example, polymerization stabilizers, colorants, microbiocidal active ingredients, additives that release fluoride ions, optical brighteners, fluorescent agents, plasticizers, transition metal redox catalysts and / or UV absorbers.
  • stabilizers such as, for example, polymerization stabilizers, colorants, microbiocidal active ingredients, additives that release fluoride ions, optical brighteners, fluorescent agents, plasticizers, transition metal redox catalysts and / or UV absorbers.
  • transition metal redox catalysts are particularly suitable as transition metal redox catalysts. These are mainly compounds of the elements copper, iron, vanadium, nickel or cobalt, with copper compounds being particularly preferred, and these metals are preferably used as compounds with good organic solubility, such as acetylacetonate, naphthenate or 2-ethylhexanoate. These catalysts accelerate the redox reaction of oxidizing and reducing agents and thus the formation of free radicals, i.e. e.g. the redox reaction of hydroperoxide and thiourea derivative.
  • Dental materials which additionally contain such a transition metal redox catalyst are preferred according to the invention. These redox catalysts are preferably used in an amount of 10-100 ppm, particularly preferably 20-80 ppm and very particularly preferably 30-80 ppm, based on the total mass of the material.
  • the materials preferably contain 10-100 ppm, particularly preferably 20-80 ppm and very particularly preferably 30-80 ppm of a transition metal redox catalyst, these quantity ranges applying to both the preferred and the particularly preferred compositions.
  • Dual-curing materials contain 0.1 to 3.0% by weight, particularly preferably 0.1 to 2.0% by weight, of peroxide (s), preferably hydroperoxide (s).
  • the dental materials according to the invention can be provided in one- or two-component form. Dual-curing materials are preferably two-component, i.e. they contain two separate components that are mixed together before use. The composition of the components is chosen so that, after mixing, materials with the overall composition defined above are obtained.
  • Dental materials which consist of the substances mentioned are very particularly preferred. Furthermore, those materials are preferred in which the individual substances are each selected from the above-mentioned preferred and particularly preferred substances. Materials that do not contain amines such as amine accelerators are particularly preferred. Materials that do not contain TEGDMA and preferably also no Bis-GMA are also preferred.
  • the dental materials according to the invention are particularly suitable as dental cements, filling composites and veneering materials and as materials for producing inlays, onlays, crowns and bridges.
  • the materials preferably only contain fillers with a maximum particle size of ⁇ 600 nm. They allow the production of dental materials with low surface roughness and high gloss as well as excellent abrasion stability.
  • the dental materials are primarily suitable for intraoral use by the dentist for the restoration of damaged teeth (clinical materials). But they can also be used extraorally, for example in the manufacture or repair of dental restorations (technical materials).
  • composites (all data in% by mass) were based on 44.5% of a silanized SiO 2 mixed oxide with a content of 30% ZrO 2 ), 20% ytterbium fluoride and 35.5% of a methacrylate mixture (20% CMP-1E, 20% GDMA, 20% TMX-UDMA, 25% UDMA and 14.5% D 3 MA and 0.5% BHT as stabilizer).
  • the components indicated in Table 1 were contained as initiator system.
  • the polymerization was carried out by irradiating from above with a polymerization lamp (LED Bluephase; Ivoclar Vivadent AG; 10 s at 650 mW / cm 2 ).
  • a polymerization lamp LED Bluephase; Ivoclar Vivadent AG; 10 s at 650 mW / cm 2 .
  • the test specimens were stored in a drying cabinet at 37 ° C. for 24 h and then the exposed upper side of the test specimens was first sanded flat with a 2,500 grit sandpaper, then a 4,000 grit sandpaper and finally polished with a polishing paste.
  • the Vickers hardness was measured on the polymerized upper side using a universal hardness tester (model ZHU0.2; Zwick / Röll). 3 individual measurements were carried out for each test specimen. The resulting mean values are given in Table 1.
  • Ivocerin ®1 [% by weight] ATU 2) / Cu 3) [% by weight] Amine [% by weight] Vickers hardness (MPa) 1 *) 0.035 0 0 92.64 ⁇ 4.3 2 0.035 1.50 / 65 0 129.1 ⁇ 7.7 3 *) 0.050 0 0 206.2 ⁇ 9.7 4th 0.050 1.50 / 65 0 242.8 ⁇ 10.1 4a *) 0 1.50 / 65 0 no polymerization 4b *) 0 1.50 / 0 0 no polymerization 5 *) 0.035 0 0.5 EMBO 4) 94.0 ⁇ 2.1 5a *) 0.035 0 1.5 EMBO 4) 98 ⁇ 11.5 6 *) 0.035 0 0.5 DABA 5) 100.0 ⁇ 5.8 6a *) 0.035 0 1.5 DABA 5) 95 ⁇ 0.5 7 *) 0.050 0 0.5 EMBO 4) 210.3 ⁇ 15.5 8 *) 0.050

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  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Animal Behavior & Ethology (AREA)
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Claims (14)

  1. Matériau dentaire polymérisable par voie radicalaire, qui contient, en tant qu'amorceur de polymérisation par voie radicalaire, une combinaison d'un dérivé de thiourée de formule
    Figure imgb0003
     dans laquelle
    - X représente un atome d'hydrogène ou une entité symbolisée par Y,
    - Y représente un groupe alkyle comportant de 1 à 8 atomes de carbone, un groupe cycloalkyle comportant 5 ou 6 atomes de carbone, un groupe alkyle comportant de 1 à 8 atomes de carbone et porteur d'un ou de substituant(s) chloro, hydroxy ou mercapto, un groupe alcényle comportant de 3 à 4 atomes de carbone, un groupe aryle comportant de 6 à 8 atomes de carbone, un groupe phényle porteur d'un ou de substituant(s) chloro, hydroxy, méthoxy ou sulfonyle, un groupe acyle comportant de 2 à 8 atomes de carbone, un groupe acyle porteur d'un ou de substituant(s) chloro ou méthoxy, un groupe aralkyle comportant de 7 à 8 atomes de carbone ou un groupe aralkyle porteur d'un ou de substituant(s) chloro ou méthoxy,
    - et Z représente une entité symbolisée par NH2, NHX ou NX2,
    d'un catalyseur redox à métal de transition et d'un composé de type bisacyl-dialkyl-germanium, étant entendu que ledit matériau dentaire contient, en tant que composé de type bisacyl-dialkyl-germanium, du bisbenzoyl-diéthyl-germanium, du bisbenzoyl-diméthyl-germanium, du bisbenzoyl-dibutyl-germanium, du bis(4-méthoxy-benzoyl)-diméthyl-germanium, du bis(4-méthoxy-benzoyl)-diéthyl-germanium, ou un mélange de ces composés.
  2. Matériau dentaire conforme à la revendication 1, qui contient, en tant que dérivé de thiourée, de la méthyl-thiourée, de l'éthyl-thiourée, de l'allyl-thiourée, de la butyl-thiourée, de l'hexyl-thiourée, de l'octyl-thiourée, de la benzyl-thiourée, de la 1,1,3-triméthyl-thiourée, de la 1,1-diallyl-thiourée, de la 1,3-diallyl-thiourée, de la 1-(pyridin-2-yl)-2-thiourée, de l'acétyl-thiourée, de la propanoyl-thiourée, de la butanoyl-thiourée, de la pentanoyl-thiourée, de l'hexanoyl-thiourée, de l'heptanoyl-thiourée, de l'octanoyl-thiourée, de la nonanoyl-thiourée, de la décanoyl-thiourée, de la benzoyl-thiourée, ou un mélange de ces composés.
  3. Matériau dentaire conforme à l'une des revendications précédentes, qui contient en outre un hydroperoxyde.
  4. Matériau dentaire conforme à la revendication 3, qui contient, en tant qu'hydroperoxyde, du 1,1,3,3-tétraméthyl-butyl-hydroperoxyde, du tertiobutyl-peroxyde, de l'hydroperoxyde de cumène, de l'hydroperoxyde de pinane, de l'hydroperoxyde de para-menthane, de l'hydroperoxyde de diisopropyl-benzène, du tertioamyl-hydroperoxyde, ou un mélange de ces composés.
  5. Matériau dentaire conforme à l'une des revendications 1 à 4, qui contient, en tant que matrice polymérisable, des monomères polymérisables par voie radicalaire ou des mélanges de monomères polymérisables par voie radicalaire, en particulier un ou plusieurs méthacrylate(s), de préférence un mélange de méthacrylates monofonctionnels et polyfonctionnels, et surtout, un mélange de méthacrylates monofonctionnels et difonctionnels.
  6. Matériau dentaire conforme à la revendication 5, qui contient un mélange de monomères comprenant au moins un monométhacrylate peu volatil, au moins un méthacrylate polyfonctionnel, de préférence difonctionnel, fortement visqueux, et au moins un méthacrylate polyfonctionnel, de préférence difonctionnel, faiblement visqueux.
  7. Matériau dentaire conforme à la revendication 6, qui contient, en tant que diméthacrylate fortement visqueux, du TMX-UDMA (un produit d'addition de HEMA et de HPMA (méthacrylate d'hydroxypropyle) avec du TMXDI (α,α,α',α'-tétraméthyl-méta-xylylène-diisocyanate)) et/ou de l'UDMA (1,6-bis[(2-méthacryloyloxy-éthoxy)-carbonylamino]-2,4,4-triméthyl-hexane ; en tant que diméthacrylate faiblement visqueux, du TCDMA (bis(méthacryloyloxy-méthyl)-tricyclo[5.2.1]décane), du GDMA (diméthacrylate de glycérol) et/ou du D3MA (diméthacrylate de décane-1,10-diol) ; et en tant que monométhacrylate peu volatil, du CMP-1E (méthacrylate de para-cumyl-phénoxy-éthylène-glycol).
  8. Matériau dentaire conforme à l'une des revendications 1 à 7, qui contient en outre une charge organique ou inorganique en particules dont la taille maximale vaut de préférence moins de 600 nm.
  9. Matériau dentaire conforme à l'une des revendications 1 à 8, qui contient
    a) de 2,0 à 20 % en poids et de préférence de 5 à 15 % en poids d'un ou de plusieurs monométhacrylate(s),
    b) de 5,0 à 60 % en poids et de préférence de 10 à 40 % en poids d'un ou de plusieurs diméthacrylate(s),
    c) de 0 à 15 % en poids et de préférence de 0 à 10 % en poids d'un ou de plusieurs monomère(s) adhésif(s) porteur(s) de groupes acides,
    d) de 20 à 90 % en poids et de préférence de 40 à 80 % en poids de charge(s),
    e) de 0,01 à 4,0 % en poids et de préférence de 0,1 à 2,0 % en poids de dérivé(s) de thiourée,
    f) de 0 à 3,0 % en poids et de préférence de 0,1 à 2,0 % en poids d'hydroperoxyde(s),
    g) de 0,001 à 1,0 % en poids et de préférence de 0,005 à 0,5 % en poids de composé(s) de type bisacyl-dialkyl-germanium,
    h) de 0,1 à 5,0 % en poids et de préférence de 0,1 à 2,0 % en poids d'adjuvant(s).
  10. Matériau dentaire conforme à la revendication 9, qui contient
    a) de 2,0 à 20 % en poids et de préférence de 5 à 15 % en poids d'un ou de plusieurs monométhacrylate(s) peu volatil(s),
    b1) de 5,0 à 25 % en poids et de préférence de 5 à 15 % en poids d'un ou de plusieurs diméthacrylate(s) fortement visqueux,
    b2) de 5 à 30 % en poids et de préférence de 10 à 20 % en poids d'un ou de plusieurs diméthacrylate(s) faiblement visqueux,
    c) de 0 à 15 % en poids et de préférence de 0 à 10 % en poids d'un ou de plusieurs monomère(s) adhésif(s) porteur(s) de groupes acides,
    d) de 20 à 90 % en poids et de préférence de 40 à 80 % en poids de charge(s),
    e) de 0,01 à 4,0 % en poids et de préférence de 0,1 à 2,0 % en poids de dérivé(s) de thiourée,
    f) de 0 à 3,0 % en poids et de préférence de 0,1 à 2,0 % en poids d'hydroperoxyde(s),
    g) de 0,001 à 1,0 % en poids et de préférence de 0,005 à 0,5 % en poids de composé(s) de type bisacyl-dialkyl-germanium,
    h) de 0,1 à 5,0 % en poids et de préférence de 0,1 à 2,0 % en poids d'adjuvant(s).
  11. Matériau dentaire conforme à l'une des revendications 1 à 10, qui contient de 10 à 100 ppm, de préférence de 20 à 80 ppm et surtout de 30 à 80 ppm de catalyseur redox à métal de transition.
  12. Matériau dentaire conforme à l'une des revendications 1 à 11, qui ne contient pas de TEGDMA, et de préférence, pas non plus de bis-GMA.
  13. Matériau dentaire conforme à l'une des revendications 1 à 12, qui ne contient pas d'amines.
  14. Utilisation d'un matériau dentaire conforme à l'une des revendications 1 à 13 en tant que ciment dentaire, composite de remplissage, matériau de placage, en tant que matériaux pour la fabrication de prothèses inlays ou onlays, de couronnes ou de bridges.
EP15710542.0A 2014-03-20 2015-03-19 Matériaux dentaires photopolymérisables à double polymérisation à base de dérivés de thio-urée et de bisacyldialkylgermanium Active EP3119377B1 (fr)

Priority Applications (1)

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PL15710542T PL3119377T3 (pl) 2014-03-20 2015-03-19 Fotopolimeryzowalne i podwójnie utwardzalne materiały stomatologiczne na bazie pochodnych tiomocznika

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EP14160824.0A EP2921154B1 (fr) 2014-03-20 2014-03-20 Matériaux dentaires photopolymérisables à double polymérisation à base de dérivés de thio-urée et de bisacyldialkylgermanium
PCT/EP2015/055858 WO2015140276A1 (fr) 2014-03-20 2015-03-19 Matériaux dentaires photopolymérisables et à polymérisation duale à base de dérivés de thio-urée

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EP15710542.0A Active EP3119377B1 (fr) 2014-03-20 2015-03-19 Matériaux dentaires photopolymérisables à double polymérisation à base de dérivés de thio-urée et de bisacyldialkylgermanium

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EP (2) EP2921154B1 (fr)
JP (1) JP6526042B2 (fr)
KR (1) KR102084827B1 (fr)
CN (1) CN106132380B (fr)
AU (1) AU2015233469B2 (fr)
CA (1) CA2941421C (fr)
ES (2) ES2622347T3 (fr)
MX (1) MX2016011950A (fr)
PL (1) PL3119377T3 (fr)
WO (1) WO2015140276A1 (fr)

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JP6793106B2 (ja) 2017-11-14 2020-12-02 株式会社ジーシー 歯科用光重合性組成物及び光重合開始剤
CN109370505A (zh) * 2018-09-21 2019-02-22 苏州吉格邦新材料科技有限公司 一种uv-化学双固化双组份胶水及其制备方法
ES2879378T3 (es) * 2019-02-07 2021-11-22 Ivoclar Vivadent Ag Materiales dentales a base de sistemas rédox con derivados de hidroperóxido de cumeno de olor reducido
ES2936645T3 (es) * 2021-02-05 2023-03-21 Ivoclar Vivadent Ag Materiales dentales a base de derivados de tiourea polimerizables
JP7090366B1 (ja) 2021-09-17 2022-06-24 Ｙａｍａｋｉｎ株式会社 歯科用表面滑沢組成物
EP4331557A1 (fr) 2022-09-01 2024-03-06 Ivoclar Vivadent AG Composition polymérisable par voie radicalaire comprenant un système initiateur redox à base de dihydropyridines
WO2024157692A1 (fr) * 2023-01-23 2024-08-02 株式会社トクヤマデンタル Ciment dentaire et kit de préparation associé

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US3991008A (en) 1974-08-12 1976-11-09 The Kendall Company Dental compositions having improved color stability
US4539382A (en) * 1981-07-29 1985-09-03 Kuraray Co., Ltd. Adhesive composition
US7275932B2 (en) 2001-09-20 2007-10-02 Pentron Clinical Technologies, Llc Self-curing system for endodontic sealant applications
WO2003057792A2 (fr) 2001-12-29 2003-07-17 3M Innovative Properties Company Composition contenant un agent reducteur polymerisable, trousse de materiel et procede
US7166651B2 (en) 2003-05-19 2007-01-23 Kerr Corporation Two-part self-adhering dental compositions
US7498367B2 (en) 2005-02-21 2009-03-03 Kerr Corporation Acid-tolerant dental composition
DE102005039590B4 (de) * 2005-08-19 2008-05-21 Heraeus Kulzer Gmbh Polymerisierbare Dentalzusammensetzung mit einem 2-Komponenten-Initiatorsystem
EP1905413A1 (fr) 2006-09-27 2008-04-02 Ivoclar Vivadent AG Compositions polymérisable avec acyl-germanium comme amorceurs
EP1905415B1 (fr) 2006-09-27 2009-07-01 Ivoclar Vivadent AG Compositions polymérisable avec acyl-germanium comme amorceurs
US8198343B2 (en) 2007-04-25 2012-06-12 Dentsply International Inc. Self-adhesive dental cement
EP2103297B1 (fr) 2008-03-20 2012-05-16 Ivoclar Vivadent AG Composition polymérisable contenant des initiateurs comprenant plusieurs atomes de Germanium
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JP5225906B2 (ja) 2009-03-25 2013-07-03 株式会社ジーシー 重合性組成物
EP2649981B1 (fr) * 2012-04-11 2018-11-21 Ivoclar Vivadent AG Compositions polymérisables avec profondeur de polymérisation élevée

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EP2921154A1 (fr) 2015-09-23
ES2907451T3 (es) 2022-04-25
US20170128328A1 (en) 2017-05-11
AU2015233469A1 (en) 2016-09-15
CN106132380B (zh) 2020-02-11
PL3119377T3 (pl) 2022-04-25
JP2017507984A (ja) 2017-03-23
US10195121B2 (en) 2019-02-05
CA2941421C (fr) 2022-08-16
AU2015233469B2 (en) 2020-01-02
JP6526042B2 (ja) 2019-06-05
MX2016011950A (es) 2016-12-05
CA2941421A1 (fr) 2015-09-24
ES2622347T3 (es) 2017-07-06
WO2015140276A1 (fr) 2015-09-24
KR20160133481A (ko) 2016-11-22
KR102084827B1 (ko) 2020-03-04
EP3119377A1 (fr) 2017-01-25
EP2921154B1 (fr) 2017-03-08
CN106132380A (zh) 2016-11-16

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